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Title: Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes

The distribution and concentration of lithium in Li-ion battery cathodes at different stages of cycling is a pivotal factor in determining battery performance. Non-uniform distribution of the transition metal cations has been shown to affect cathode performance; however, the Li is notoriously challenging to characterize with typical high-spatial-resolution imaging techniques. Here, for the first time, laser–assisted atom probe tomography is applied to two advanced Li-ion battery oxide cathode materials—layered Li1.2Ni0.2Mn0.6O2 and spinel LiNi0.5Mn1.5O4—to unambiguously map the three dimensional (3D) distribution of Li at sub-nanometer spatial resolution and correlate it with the distribution of the transition metal cations (M) and the oxygen. The as-fabricated layered Li1.2Ni0.2Mn0.6O2 is shown to have Li-rich Li2MO3 phase regions and Li-depleted Li(Ni0.5Mn0.5)O2 regions while in the cycled layered Li1.2Ni0.2Mn0.6O2 an overall loss of Li and presence of Ni rich regions, Mn rich regions and Li rich regions are shown in addition to providing the first direct evidence for Li loss on cycling of layered LNMO cathodes. The spinel LiNi0.5Mn1.5O4 cathode is shown to have a uniform distribution of all cations. These results were additionally validated by correlating with energy dispersive spectroscopy mapping of these nanoparticles in a scanning transmission electron microscope. Thus, we have opened themore » door for probing the nanoscale compositional fluctuations in crucial Li-ion battery cathode materials at an unprecedented spatial resolution of sub-nanometer scale in 3D which can provide critical information for understanding capacity decay mechanisms in these advanced cathode materials.« less
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [4] ;  [5]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. FEI Company, Hillsboro, OR (United States)
  3. Qatar Environment and Energy Research Institute, Doha (Qatar)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Qatar Environment and Energy Research Institute, Doha (Qatar)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 2041-1723; 48658
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2041-1723
Nature Publishing Group
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Environmental Molecular Sciences Laboratory; chemical sciences; materials science; nanotechnology